Search results for: photocatalytic properties

Authors: Ksenija Milošević, Davor Lončarević, Tihana Mudrinić, Jasmina Dostanić

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Heterogeneous photocatalytic processes have gained growing interest as an efficient method to generate hydrogen by using clean energy sources and degrading various organic pollutants. The main obstacles that restrict efficient photoactivity are narrow light-response range and high rates of charge carrier recombination. The formation of heterojunction by combining a semiconductor with low VB and a semiconductor with high CB and a suitable band gap was found to be an efficient method to prepare more sensible materials with improved charge separation, appropriate oxidation and reduction ability, and enhanced visible-light harvesting. In our research, various binary heterojunction systems based on the wide-band gap (TiO₂) and narrow bandgap (g-C₃N₄, CuO, and Co₂O₃) photocatalyst were studied. The morphology, optical, and electrochemical properties of the photocatalysts were analyzed by X-ray diffraction (XRD), scanning electron microscopy (FE-SEM), N₂ physisorption, diffuse reflectance measurements (DRS), and Mott-Schottky analysis. The photocatalytic performance of the synthesized catalysts was tested in single and simultaneous systems. The synthesized photocatalysts displayed good adsorption capacity and enhanced visible-light photocatalytic performance. The mutual interactions of pollutants on their adsorption and degradation efficiency were investigated. The interfacial connection between photocatalyst constituents and the mechanism of the transport pathway of photogenerated charge species was discussed. A radical scavenger study revealed the interaction mechanisms of the photocatalyst constituents in single and multiple pollutant systems under solar and visible light irradiation, indicating the type of heterojunction system (Z scheme or type II).

Keywords: bandgap alignment, heterojunction, photocatalysis, reaction mechanism

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Authors: I. Ben Kaddour, S. Larbaoui

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Since their first synthesis, the Silicoaluminophosphates materials have proved their efficiency as a good adsorbent and catalyst in several environmental and energetic applications. In this work, the photocatalytic hydrogen production from water splitting reactions has been conducted under visible radiations in the presence of a series of iron and/or titanium-containing microporous silico-alumino-phosphates materials synthesized by hydrothermal method, using triethylamine as an organic structuring agent to obtain the AFI structure type. These photo-catalysts were then characterized by various physicochemical methods to determine their structural, textural and morphological properties such as X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) coupled with X rays microanalysis, nitrogen adsorption measurements, UV-visible diffuse reflectance spectroscopy (UV-Vis-DRS), and X-rays photoelectron spectroscopy (XPS) and the analysis revealed that these materials have significant photocatalytic properties. The hydrogen production process has been followed by photoelectrochemical characterization (PEC). The results showed that hydrogen is the only gas produced, and the reaction takes place in the conduction band where water is reduced to hydrogen. The electron recombination has also been avoided, as holes are entrapped using hole scavengers. In addition, these catalysts have been shown to remain stable during reuse for up to five cycles.

Keywords: photocatalysis, SAPO-5, hydrothermal synthesis, hydrogen production

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Authors: Rafid Mueen, Konstantin Konstantinov, Micheal Lerch, Zhenxiang Cheng

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In the past two decades, the concern for skin protection from ultraviolet (UV) radiation has attracted considerable attention due to the increased intensity of UV rays that can reach the Earth’s surface as a result of the breakdown of ozone layer. Recently, UVA has also attracted attention, since, in comparison to UVB, it can penetrate deeply into the skin, which can result in significant health concerns. Sunscreen agents are one of the significant tools to protect the skin from UV irradiation, and it is either organic or in organic. Developing of inorganic UV blockers is essential, which provide efficient UV protection over a wide spectrum rather than organic filters. Furthermore inorganic UV blockers are good comfort, and high safety when applied on human skin. Inorganic materials can absorb, reflect, or scatter the ultraviolet radiation, depending on their particle size, unlike the organic blockers, which absorb the UV irradiation. Nowadays, most inorganic UV-blocking filters are based on (TiO2) and ZnO). ZnO can provide protection in the UVA range. Indeed, ZnO is attractive for in sunscreen formulization, and this relates to many advantages, such as its modest refractive index (2.0), absorption of a small fraction of solar radiation in the UV range which is equal to or less than 385 nm, its high probable recombination of photogenerated carriers (electrons and holes), large direct band gap, high exciton binding energy, non-risky nature, and high tendency towards chemical and physical stability which make it transparent in the visible region with UV protective activity. A significant issue for ZnO use in sunscreens is that it can generate ROS in the presence of UV light because of its photocatalytic activity. Therefore it is essential to make a non-photocatalytic material through modification by other metals. Several efforts have been made to deactivate the photocatalytic activity of ZnO by using inorganic surface modifiers. The doping of ZnO by different metals is another way to modify its photocatalytic activity. Recently, successful doping of ZnO with different metals such as Ce, La, Co, Mn, Al, Li, Na, K, and Cr by various procedures, such as a simple and facile one pot water bath, co-precipitation, hydrothermal, solvothermal, combustion, and sol gel methods has been reported. These materials exhibit greater performance than undoped ZnO towards increasing the photocatalytic activity of ZnO in visible light. Therefore, metal doping can be an effective technique to modify the ZnO photocatalytic activity. However, in the current work, we successfully reduce the photocatalytic activity of ZnO through Na doped ZnO fabricated via sol-gel and hydrothermal methods.

Keywords: photocatalytic, ROS, UVA, ZnO

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Authors: Yasar N. Kavil, Yasser A. Shaban, Radwan K. Al Farawati, Mohamed I. Orif, Shahed U. M. Khanc

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Photocatalytic way of reduction of CO₂ in polluted seawater into chemical fuel, methanol, was successfully gained over Cu/C-co-doped TiO₂ nanoparticles under UV and natural sunlight. A homemade stirred batch annular reactor was used to carry out the photocatalytic reduction experiments. Photocatalysts with various Cu loadings (0, 0.5, 1, 3, 5 and 7 wt.%) were synthesized by the sol-gel procedure and were characterized by XRD, SEM, UV–Vis, FTIR, and XPS. The photocatalytic production of methanol was promoted by the co-doping with C and Cu into TiO₂. This improvement was attributed to the modification of bandgap energy and the hindrance of the charges recombination. The polluted seawater showing the yield depended on its background hydrographic parameters. We assessed two types of polluted seawater system, the observed yield was 2910 and 990 µmol g⁻¹ after 5 h of illumination under UV and natural sunlight respectively in system 1 and the corresponding yield in system 2 was 2250 and 910 µmol g⁻¹ after 5 h of illumination. The production of methanol in the case of oxygen-depleted water was low, this is mainly attributed to the competition of methanogenic bacteria over methanol production. The results indicated that the methanol yield produced by Cu-C/TiO₂ was much higher than those of carbon-modified titanium oxide (C/TiO₂) and Degussa (P25-TiO₂). Under the current experimental condition, the optimum loading was achieved by the doping of 3 wt % of Cu. The highest methanol yield was obtained over 1 g L-1 of 3wt% Cu/C-TiO₂.

Keywords: CO₂ photoreduction, copper, Cu/C-co-doped TiO₂, methanol, seawater

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Authors: Maali-Amel Mersel, Lajos Fodor, Otto Horvath

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Photocatalytic H₂ production by H₂S decomposition is regarded to be an environmentally friendly process to produce carbon-free energy through direct solar energy conversion. For this purpose, sulphide-based materials, as photocatalysts, were widely used due to their excellent solar spectrum responses and high photocatalytic activity. The loading of proper co-catalysts that are based on cheap and earth-abundant materials on those semiconductors was shown to play an important role in the improvement of their efficiency. In this research, CdS-ZnS composite was studied because of its controllable band gap and excellent performance for H₂ evolution under visible light irradiation. The effects of the modification of this photocatalyst with different types of materials and the influence of the preparation parameters on its H₂ production activity were investigated. The CdS-ZnS composite with an enhanced photocatalytic activity for H₂ production was synthesized from ammine complexes. Two types of modification were used: compounds of Ni-group metals (NiS, PdS, and Pt) were applied as co-catalyst on the surface of CdS-ZnS semiconductor, while NiS, MnS, CoS, Ag₂S, and CuS were used as a dopant in the bulk of the catalyst. It was found that 0.1% of noble metals didn’t remarkably influence the photocatalytic activity, while the modification with 0.5% of NiS was shown to be more efficient in the bulk than on the surface. The modification with other types of metals results in a decrease of the rate of H₂ production, while the co-doping seems to be more promising. The preparation parameters (such as the amount of ammonia to form the ammine complexes, the order of the preparation steps together with the hydrothermal treatment) were also found to highly influence the rate of H₂ production. SEM, EDS and DRS analyses were made to reveal the structure of the most efficient photocatalysts. Moreover, the detection of the conduction band electron on the surface of the catalyst was also investigated. The excellent photoactivity of the CdS-ZnS catalysts with and without modification encourages further investigations to enhance the hydrogen generation by optimization of the reaction conditions.

Keywords: H₂S, photoactivity, photocatalytic H₂ production, CdS-ZnS

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Authors: Syed Najeeb-Uz-Zaman Haider, Yang Juan

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Antibiotic overuse raises environmental concerns, boosting the demand for efficient removal from pharmaceutical wastewater. Photocatalysis, particularly using semiconductor photocatalysts, offers a promising solution and garners significant scientific interest. In this study, a Z-scheme 0.15BWO/CCN heterojunction was developed, analyzed, and employed for the photocatalytic degradation of tetracycline hydrochloride (TC) under visible light. The study revealed that the dosage of 0.15BWO@CCN and the presence of coexisting ions significantly influenced the degradation efficiency, achieving up to 87% within 20 minutes under optimal conditions (at pH 9-11/strongly basic conditions) while maintaining 84% efficiency under standard conditions (unaltered pH). Photoinduced electrons gathered on the conduction band of BWO while holes accumulated on the valence band of CCN, creating more favorable conditions to produce superoxide and hydroxyl radicals. Additionally, through comprehensive experimental analysis, the degradation pathway and mechanism were thoroughly explored. The superior photocatalytic performance of 0.15BWO@CCN was attributed to its Z-scheme heterojunction structure, which significantly reduced the recombination of photoinduced electrons and holes. The radicals produced were identified using ESR, and their involvement in tetracycline degradation was further analyzed through active species trapping experiments.

Keywords: CCN, Bi₂WO₆, TC, photocatalytic degradation, heterojunction

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Authors: H. F. Shi, C. L. Zhang

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Visible-light-responsive g-C3N4/NaNbO3 nanowires photocatalysts were fabricated by introducing polymeric g-C3N4 on NaNbO3 nanowires. The microscopic mechanisms of interface interaction, charge transfer and separation, as well as the influence on the photocatalytic activity of g-C3N4/NaNbO3 composite were systematic investigated. The HR-TEM revealed that an intimate interface between C3N4 and NaNbO3 nanowires formed in the g-C3N4/NaNbO3 heterojunctions. The photocatalytic performance of photocatalysts was evaluated for CO2 reduction under visible-light illumination. Significantly, the activity of g-C3N4/NaNbO3 composite photocatalyst for photoreduction of CO2 was higher than that of either single-phase g-C3N4 or NaNbO3. Such a remarkable enhancement of photocatalytic activity was mainly ascribed to the improved separation and transfer of photogenerated electron-hole pairs at the intimate interface of g-C3N4/NaNbO3 heterojunctions, which originated from the well-aligned overlapping band structures of C3N4 and NaNbO3. Pt loaded NaNbO3-xNx (Pt-NNON), a visible-light-sensitive photocatalyst, was synthesized by an in situ photodeposition method from H2PtCl6•6H2O onto NaNbO3-xNx (NNON) sample. Pt-NNON exhibited a much higher photocatalytic activity for gaseous 2-propanol (IPA) degradation under visible-light irradiation in contrast to NNON. The apparent quantum efficiency (AQE) of Pt-NNON sample for IPA photodegradation achieved up to 8.6% at the wavelength of 419 nm. The notably enhanced photocatalytic performance was attributed to the promoted charge separation and transfer capability in the Pt-NNON system. This work suggests that surface nanosteps possibly play an important role as an electron transfer at high way, which facilitates to the charge carrier collection onto Pt rich zones and thus suppresses recombination between photogenerated electrons and holes. This method can thus be considered as an excellent strategy to enhance photocatalytic activity of organic decomposition in addition to the commonly applied noble metal doping method.

Keywords: CO2 reduction, NaNbO3, nanowires, g-C3N4

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Authors: Hamsasew Hankebo Lemago, Dóra Hessz, Zoltán Erdélyi, Imre Miklós Szilágyi

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Metal oxide inverse opals are a unique class of photocatalysts with a hierarchical structure that mimics the natural opal gemstone. They are composed of a network of interconnected pores, which provides a large surface area and efficient pathways for the transport of light and reactants. Atomic layer deposition (ALD) is a versatile technique for the synthesis of high-precision metal oxide thin films, including inverse opals. ALD allows for precise control over the thickness, composition, and morphology of the synthesized films, making it an ideal technique for the fabrication of photocatalysts with tailored properties. In this study, we report the synthesis of TiO2, ZnO, and Al2O3 inverse opal photocatalysts using thermal or plasma-enhanced ALD. The synthesized photocatalysts were characterized using a variety of techniques, including scanning electron microscopy (SEM)-energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Raman spectroscopy, photoluminescence (PL), ellipsometry, and UV-visible spectroscopy. The results showed that the ALD-synthesized metal oxide inverse opals had a highly ordered structure and a tunable pore size. The PL spectroscopy results showed low recombination rates of photogenerated electron-hole pairs, while the ellipsometry and UV-visible spectroscopy results showed tunable optical properties and band gap energies. The photocatalytic activity of the samples was evaluated by the degradation of methylene blue under visible light irradiation. The results showed that the ALD-synthesized metal oxide inverse opals exhibited high photocatalytic activity, even under visible light irradiation. The composites photocatalysts showed even higher activity than the individual metal oxide inverse opals. The enhanced photocatalytic activity of the composites can be attributed to the synergistic effect between the different metal oxides. For example, Al2O3 can act as a charge carrier scavenger, which can reduce the recombination of photogenerated electron-hole pairs. The ALD-synthesized metal oxide inverse opals and their composites are promising photocatalysts for a variety of applications, such as wastewater treatment, air purification, and energy production. For example, they can be used to remove organic pollutants from wastewater, decompose harmful gases in the air, and produce hydrogen fuel from water.

Keywords: ALD, metal oxide inverse opals, composites, photocatalysis

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Authors: M. S. Abd El-Sadek, Mahmoud A. Omar, Gharib M. Taha

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Photodegradation of methylene blue in the presence of tin dioxide (SnO₂) nanoparticles under solar light irradiation are known to be an effective photocatalytic process. In this study, pure and silver (Ag) doped tin dioxide (SnO₂) nanoparticles were prepared at calcination temperature (800ºC) by a modified sol-gel method and studied for their photocatalytic activity with methylene blue as a test contaminant. The characterization of undoped and doped SnO₂ photocatalyst was studied by X-rays diffraction patterns (XRD), transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FT-IR) and Energy Dispersive X-ray Microanalysis (EDX). The catalytic degradation of methylene blue in aqueous media was studied using UV-Vis spectrophotometer to monitor the degradation process by measuring its absorption spectra. The main absorption peak of methylene blue is observed at λ= 664 nm. The change in the percent of silver in the catalyst affects the photoactivity of SnO₂ on the degradation of methylene blue. The photoactivity of pure SnO₂ was found to be a maximum at dose 0.2 gm of the catalyst with 100 ml of 5 ppm methylene blue in the water. Within 210 min of photodegradation (under sunlight) after leaving the reaction for 90 minutes in the dark to avoid the effect of adsorption, the pure SnO₂ at calcination temperature 800ºC exhibited the best photocatalytic degradation with removal percentage of 93.66% on methylene blue degradation under solar light.

Keywords: SnO₂ nanoparticles, methylene blue degradation, photocatalysis, silver doped-SnO₂

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Authors: S. V. Prabhakar Vattikuti, Chan Byon

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In this paper, we report a facile synthetic strategy of randomly disturbed Bi₂S₃ nanorods on WS₂ nanosheets, which are synthesized via a controlled hydrothermal method without surfactant under an inert atmosphere. We developed a simple hydrothermal method for the formation of heterostructured of Bi₂S₃/WS₂ with a large scale (>95%). The structural features, composition, and morphology were characterized by XRD, SEM-EDX, TEM, HRTEM, XPS, UV-vis spectroscopy, N₂ adsorption-desorption, and TG-DTA measurements. The heterostructured Bi₂S₃/WS₂ composite has significant photocatalytic efficiency toward the photodegradation of organic dye. The time-dependent UV-vis absorbance spectroscopy measurement was consistent with the enhanced photocatalytic degradation of rhodamine B (RhB) under visible light irradiation with the diminishing carrier recombination for the Bi₂S₃/WS₂ photocatalyst. Due to their marked synergistic effects, the supported Bi₂S₃ nanorods on WS₂ nanosheet heterostructures exhibit significant visible-light photocatalytic activity and stability for the degradation of RhB. A possible reaction mechanism is proposed for the Bi₂S₃/WS₂ composite.

Keywords: photocatalyst, heterostructures, transition metal disulfides, organic dye, nanorods

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Authors: Ghadeer Jalloul, Nour Hijazi, Cassia Boyadjian, Hussein Awala, Mohammad N. Ahmad, ‎Ahmad Albadarin

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In this study, we applied Fe-sensitized TiO₂ supported over embryonic Beta zeolite (BEA) zeolite ‎for the photocatalytic degradation of Tetracycline (TC) antibiotic under visible light. Four different ‎samples having 20, 40, 60, and 100% w/w as a ratio of TiO₂/BEA were prepared. The ‎immobilization of solgel TiO₂ (33 m²/g) over BEA (390 m²/g) increased its surface area to (227 ‎m²/g) and enhanced its adsorption capacity from 8% to 19%. To expand the activity of TiO₂ ‎photocatalyst towards the visible light region (λ>380 nm), we explored two different metal ‎sensitization techniques with Iron ions (Fe³⁺). In the ion-exchange method, the substitutional cations ‎in the zeolite in TiO₂/BEA were exchanged with (Fe³⁺) in an aqueous solution of FeCl₃. In the ‎doping technique, solgel TiO₂ was doped with (Fe³⁺) from FeCl₃ precursor during its synthesis and ‎before its immobilization over BEA. (Fe-TiO₂/BEA) catalysts were characterized using SEM, XRD, ‎BET, UV-VIS DRS, and FTIR. After testing the performance of the various ion-exchanged catalysts ‎under blue and white lights, only (Fe-TiO₂/BEA 60%) showed better activity as compared to pure ‎TiO₂ under white light with 100 ppm initial catalyst concentration and 20 ppm TC concentration. As ‎compared to ion-exchanged (Fe-TiO₂/BEA), doped (Fe-TiO₂/BEA) resulted in higher photocatalytic ‎efficiencies under blue and white lights. The 3%-Fe-doped TiO₂/BEA removed 92% of TC ‎compared to 54% by TiO₂ under white light. The catalysts were also tested under real solar ‎irradiations. This improvement in the photocatalytic performance of TiO₂ was due to its higher ‎adsorption capacity due to BEA support combined with the presence of Iron ions that enhance the ‎visible light absorption and minimize the recombination effect by the charge carriers. ‎

Keywords: Tetracycline, photocatalytic degradation, immobilized TiO₂, zeolite, iron-doped TiO₂, ion-exchange

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Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

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Authors: Navven Desai, Veena Soraganvi

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Heavy metals such as lead, cadmium and mercury do not have biological significance hence they are known to be extremely toxic heavy metals. Water contains various heavy metals like Cadmium (Cd), Chromium (Cr), Copper (Cu), Nickel (Ni), Arsenic (As), Lead (Pb), and Zinc (Zn) etc., when it gets polluted with industrial waste water. These heavy metals cause various health effects even at low concentration when consumed by humans. Most of the heavy metals are poisonous to living organisms. Heavy metals are non-degradable and are preserved in the environment through bioaccumulation. Therefore removal of heavy metals from water is necessary. In recent years, a great deal of attentions has been focused on to the application of nanosized metal oxides to treat heavy metals, especially titanium oxides, ferric oxides, manganese oxides, aluminium oxides and magnesium oxides as adsorbent and photocatalyst. TiO2 based photocatalysts have attracted continuously increasing attention because of the excellent properties such as high light -conversion efficiency, chemical stability, nontoxic nature, low cost. The catalyst displays high photocatalytic activity because of its large surface area. In this study, the photocatalytic degradation of Lead (Pb) from aqueous solution was investigated in natural sunlight by using TiO2 as Nanomaterial. This study was performed at laboratory scale. All the experiments were carried out in the batch process. The concentration of lead was constant (25mg/lit) in the experiment and effect of titanium dioxide dose and pH were varied to study the removal efficiency of the lead by adsorption. Further study was performed on the dependence of photocatalytic reaction on the reaction temperature. The aqueous solution was prepared by Lead metal powder. TiO2 photo catalyst nanopowder used was Sisco-74629 grade. The heavy metal is analyzed with VARIAN AA 240 atomic adsorption spectrophotometer. The study shows, with increasing TiO2 dose and pH the lead removal increases. According to study, it can be concluded that the utilization of titanium dioxide accounted for higher efficiency in the removal of lead from aqueous solution.

Keywords: adsorption, heavy metals, nanomaterial, photocatalysis

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Authors: Jonjaua Ranogajec, Ognjen Rudic, Snezana Pasalic, Snezana Vucetic, Damir Cjepa

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The paper involves a chain of activities from synthesis, establishment of the methodology for characterization and testing of novel protective materials through the pilot production and application on model supports. It summarizes the results regarding the development of the pilot production protocol for newly developed self-cleaning materials. The optimization of the production parameters was completed in order to improve the most important functional properties (mineralogy characteristics, particle size, self-cleaning properties and photocatalytic activity) of the newly designed nanocomposite material.

Keywords: pilot production, self-cleaning materials, compatibility, cultural heritage

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Authors: Seyed Mohsen Mousavi, Ali Reza Mahjoub, Bahjat Afshari Razani

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In this work, Fe/ZnO hollow spherical structures with high surface area using the template glucose was prepared by the hydrothermal method using an ultrasonic bath at room temperature was produced and were identified by FT-IR, XRD, FE-SEM and BET. The photocatalytic activity of synthesized spherical Fe/ZnO hollow sphere were studied in the destruction of Congo Red and Methylene Blue as Azo dyes. The results showed that the photocatalytic activity of Fe/ZnO hollow spherical structures is improved compared with ZnO hollow sphere and other morphologys.

Keywords: azo dyes, Fe/ZnO hollow sphere, hollow sphere nanostructures, photocatalyst

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Authors: Yuvraj S. Malghe, Atul B. Lavand

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In recent years, semiconductor photocatalytic degradation processes have attracted a lot of attention and are used widely for the destruction of organic pollutants present in waste water. Among various semiconductors, titanium dioxide (TiO2) is the most popular photocatalyst due to its excellent chemical stability, non-toxicity, relatively low cost and high photo-oxidation power. It has been known that zinc oxide (ZnO) with band gap energy 3.2 eV is a suitable alternative to TiO2 due to its high quantum efficiency, however it corrodes in acidic medium. Unfortunately TiO2 and ZnO both are active only in UV light due to their wide band gaps. Sunlight consist about 5-7% UV light, 46% visible light and 47% infrared radiation. In order to utilize major portion of sunlight (visible spectrum), it is necessary to modify the band gap of TiO2 as well as ZnO. This can be done by several ways such as semiconductor coupling, doping the material with metals/non metals. Doping of TiO2 using transition metals like Fe, Co and non-metals such as N, C or S extends its absorption wavelengths from UV to visible region. In the present work, we have synthesized ZnO-TiO2 nanocomposite using reverse microemulsion method. Visible light photocatalytic activity of synthesized nanocomposite was investigated for degradation of aqueous solution of malachite green (MG). To increase the photocatalytic activity of ZnO-TiO2 nanocomposite, it is decorated with C and Fe. Pure, carbon (C) doped and carbon, iron(C, Fe) co-doped nanosized ZnO-TiO2 nanocomposites were synthesized using reverse microemulsion method. These composites were characterized using, X-ray diffraction (XRD), Energy dispersive X-ray spectroscopy (EDX), Scanning electron microscopy (SEM), UV visible spectrophotometery and X-ray photoelectron spectroscopy (XPS). Visible light photocatalytic activities of synthesized nanocomposites were investigated for degradation of aqueous malachite green (MG) solution. C, Fe co-doped ZnO-TiO2 nanocomposite exhibit better photocatalytic activity and showed threefold increase in photocatalytic activity. Effect of amount of catalyst, pH and concentration of MG solution on the photodegradation rate is studied. Stability and reusability of photocatalyst is also studied. C, Fe decorated ZnO-TiO2 nanocomposite shows threefold increase in photocatalytic activity.

Keywords: malachite green, nanocomposite, photocatalysis, titanium dioxide, zinc oxide

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Authors: Z. Karahaliloğlu, C. Hacker, M. Demirbilek, G. Seide, E. B. Denkbaş, T. Gries

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Currently, textile industry has played an important role in world’s economy, especially in developing countries. Dyes and pigments used in textile industry are significant pollutants. Most of theirs are azo dyes that have chromophore (-N=N-) in their structure. There are many methods for removal of the dyes from wastewater such as chemical coagulation, flocculation, precipitation and ozonation. But these methods have numerous disadvantages and alternative methods are needed for wastewater decolorization. Titanium-mediated photodegradation has been used generally due to non-toxic, insoluble, inexpensive, and highly reactive properties of titanium dioxide semiconductor (TiO2). Melt electrospinning is an attractive manufacturing process for thin fiber production through electrospinning from PP (Polyprophylene). PP fibers have been widely used in the filtration due to theirs unique properties such as hydrophobicity, good mechanical strength, chemical resistance and low-cost production. In this study, we aimed to investigate the effect of titanium nanoparticle localization and amine modification on the dye degradation. The applicability of the prepared chemical activated composite and pristine fabrics for a novel treatment of dyeing wastewater were evaluated.In this study, a photocatalyzer material was prepared from nTi (titanium dioxide nanoparticles) and PP by a melt-electrospinning technique. The electrospinning parameters of pristine PP and PP/nTi nanocomposite fabrics were optimized. Before functionalization with nTi, the surface of fabrics was activated by a technique using glutaraldehyde (GA) and polyethyleneimine to promote the dye degredation. Pristine PP and PP/nTi nanocomposite melt-electrospun fabrics were characterized using scanning electron microscopy (SEM) and X-Ray Photon Spectroscopy (XPS). Methyl orange (MO) was used as a model compound for the decolorization experiments. Photocatalytic performance of nTi-loaded pristine and nanocomposite melt-electrospun filters was investigated by varying initial dye concentration 10, 20, 40 mg/L). nTi-PP composite fabrics were successfully processed into a uniform, fibrous network of beadless fibers with diameters of 800±0.4 nm. The process parameters were determined as a voltage of 30 kV, a working distance of 5 cm, a temperature of the thermocouple and hotcoil of 260–300 ºC and a flow rate of 0.07 mL/h. SEM results indicated that TiO2 nanoparticles were deposited uniformly on the nanofibers and XPS results confirmed the presence of titanium nanoparticles and generation of amine groups after modification. According to photocatalytic decolarization test results, nTi-loaded GA-treated pristine or nTi-PP nanocomposite fabric filtern have superior properties, especially over 90% decolorization efficiency at GA-treated pristine and nTi-PP composite PP fabrics. In this work, as a photocatalyzer for wastewater treatment, surface functionalized with nTi melt-electrospun fabrics from PP were prepared. Results showed melt-electrospun nTi-loaded GA-tretaed composite or pristine PP fabrics have a great potential for use as a photocatalytic filter to decolorization of wastewater and thus, requires further investigation.

Keywords: titanium oxide nanoparticles, polyprophylene, melt-electrospinning

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Authors: Myriam Ben Said, Dhekra Trabelsi, Faouzi Achouri, Marwa Ben Saad, Latifa Bousselmi, Ahmed Ghrabi

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This present study suggests the use of biological and natural bactericide, cheap, safe to handle, natural, environmentally benign agents to enhance the conventional wastewater treatment process. In the same sense, to highlight the enhancement of wastewater photocatalytic treatability, we were used virulent bacteriophage(s) and essential oils (EOs). The pre-phago-treatment of wastewater with lytic phage(s), leads to a decrease in bacterial density and, consequently, limits the establishment of intercellular communication (QS), thus preventing biofilm formation and inhibiting the expression of other virulence factors after photocatalysis. Moreover, to increase the photocatalytic efficiency, we were added to the secondary treated wastewater 1/1000 (w/v) of EO of thyme (T. vulgaris). This EO showed in vitro an anti-biofilm activity through the inhibition of plonctonic cell mobility and their attachment on an inert surface and also the deterioration of the sessile structure. The presence of photoactivatable molecules (photosensitizes) in this type of oil allows the optimization of photocatalytic efficiency without hazards relayed to dyes and chemicals reagent. The use of ‘biological and natural tools’ in combination with usual water treatment process can be considered as a safety procedure to reduce and/or to prevent the recontamination of treated water and also to prevent the re-expression of virulent factors by pathogenic bacteria such as biofilm formation with friendly processes.

Keywords: biofilm, essential oil, optimization, phage, photocatalysis, wastewater

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Authors: Hamsasew Hankebo Lemago, Dóra Hessz, Tamás Igricz, Zoltán Erdélyi, , Imre Miklós Szilágyi

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Metal oxide inverse opals are a promising class of photocatalysts with a unique hierarchical structure. Atomic layer deposition (ALD) is a versatile technique for the synthesis of high-precision metal oxide thin films, including inverse opals. In this study, we report the synthesis of TiO₂, ZnO, and Al₂O₃ inverse opal and their composites photocatalysts using thermal or plasma-enhanced ALD. The synthesized photocatalysts were characterized using a variety of techniques, including scanning electron microscopy (SEM)-energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Raman spectroscopy, photoluminescence (PL), ellipsometry, and UV-visible spectroscopy. The results showed that the ALD-synthesized metal oxide inverse opals had a highly ordered structure and a tunable pore size. The PL spectroscopy results showed low recombination rates of photogenerated electron-hole pairs, while the ellipsometry and UV-visible spectroscopy results showed tunable optical properties and band gap energies. The photocatalytic activity of the samples was evaluated by the degradation of methylene blue under visible light irradiation. The results showed that the ALD-synthesized metal oxide inverse opals exhibited high photocatalytic activity, even under visible light irradiation. The composites photocatalysts showed even higher activity than the individual metal oxide inverse opals. The enhanced photocatalytic activity of the composites can be attributed to the synergistic effect between the different metal oxides. For example, Al₂O₃ can act as a charge carrier scavenger, which can reduce the recombination of photogenerated electron-hole pairs. The ALD-synthesized metal oxide inverse opals and their composites are promising photocatalysts for a variety of applications, such as wastewater treatment, air purification, and energy production. The ALD-synthesized metal oxide inverse opals and their composites are promising photocatalysts for a variety of applications, such as wastewater treatment, air purification, and energy production.

Keywords: ALD, metal oxide inverse opals, photocatalysis, composites

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Authors: R. Yuvakkumar, S. I. Hong

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Visible light driven monoclinic α-Bi2O3 photocatalyst was synthesized employing green synthesis method using rambutan peel wastes. 10 ml rambutan extract was added to 50 ml of 0.1M Bi(NO3)3 under stirring at about 80°C for 2 hours. The centrifuged and dried product was calcinated in a muffle furnace at 450°C to get pure α-Bi2O3. The characterized product photocatalytic activity was evaluated employing methyl orange (MeO) as model pollutant with 10 mg l-1 concentration at pH 7. The obtained product optical absorption edges located at 484 nm clearly revealed the photocatalyst excitation by visible light irradiation. The obtained yellow color photocatalyst accord with its strong absorption spectrum revealed the visible light absorption due to the band gap transition. The band gap energy of α-Bi2O3 was estimated to be 2.81 eV indicating the absorption of α-Bi2O3 in visible light region. The photocatalytic results of MeO degradation revealed that green synthesized Bi2O3 can effectively degrade 92% MeO within 240 min under visible light (>400 nm), which is slightly increased to that of chemically synthesized Bi2O3 (90%).

Keywords: green synthesis, bismuth oxide, photocatalytic activity, nano

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Authors: Totsaporn Suwannaruang, Kitirote Wantala

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The purposes of this research were to synthesize titanium dioxide photocatalyst doped with nitrogen (N-doped TiO₂) by hydrothermal method and to test the photocatalytic degradation of paraquat under UV and visible light illumination. The effect of calcination treatment temperature on their physical and chemical properties and photocatalytic efficiencies were also investigated. The characterizations of calcined N-doped TiO₂ photocatalysts such as specific surface area, textural properties, bandgap energy, surface morphology, crystallinity, phase structure, elements and state of charges were investigated by Brunauer, Emmett, Teller (BET) and Barrett, Joyner, Halenda (BJH) equations, UV-Visible diffuse reflectance spectroscopy (UV-Vis-DRS) by using the Kubelka-Munk theory, Wide-angle X-ray scattering (WAXS), Focussed ion beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), respectively. The results showed that the effect of calcination temperature was significant on surface morphology, crystallinity, specific surface area, pore size diameter, bandgap energy and nitrogen content level, but insignificant on phase structure and oxidation state of titanium (Ti) atom. The N-doped TiO₂ samples illustrated only anatase crystalline phase due to nitrogen dopant in TiO₂ restrained the phase transformation from anatase to rutile. The samples presented the nanorice-like morphology. The expansion on the particle was found at 650 and 700°C of calcination temperature, resulting in increased pore size diameter. The bandgap energy was determined by Kubelka-Munk theory to be in the range 3.07-3.18 eV, which appeared slightly lower than anatase standard (3.20 eV), resulting in the nitrogen dopant could modify the optical absorption edge of TiO₂ from UV to visible light region. The nitrogen content was observed at 100, 300 and 400°C only. Also, the nitrogen element disappeared at 500°C onwards. The nitrogen (N) atom can be incorporated in TiO₂ structure with the interstitial site. The uncalcined (100°C) sample displayed the highest percent paraquat degradation under UV and visible light irradiation due to this sample revealed both the highest specific surface area and nitrogen content level. Moreover, percent paraquat removal significantly decreased with increasing calcination treatment temperature. The nitrogen content level in TiO₂ accelerated the rate of reaction with combining the effect of the specific surface area that generated the electrons and holes during illuminated with light. Therefore, the specific surface area and nitrogen content level demonstrated the important roles in the photocatalytic activity of paraquat under UV and visible light illumination.

Keywords: restraining phase transformation, interstitial site, chemical charge state, photocatalysis, paraquat degradation

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Authors: B. Benalioua, I. Benyamina, A. Bentouami, B. Boury

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The objective of this study is based on the synthesis of a new photocatalyst based on TiO2 and its application in the photo-degradation of an acid dye under the visible light. The material obtained was characterized by different techniques like diffuse reflectance UV–Vis spectroscopy (DRS), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic efficiency of the Bi, N co-doped TiO2 treated at 600°C for 1 h was tested on the Indigo Carmine under the irradiation of visible light and compared with that of the commercial titanium oxide TiO2-P25 (Degussa). The XRD characterization of the material Bi -N- TiO2 (600°C) revealed the presence of the anatase phase and the absence of the rutile phase in comparison of the TiO2 P25 diffractogram. Characterization by UV- visible diffuse reflection (DRS) material showed that the Bi-N-TiO2 exhibits redshift (move visible) relative to commercial titanium oxide TiO2-P25, this property promises a photocatalytic activity of Bi-N-TiO2 under visible light. Indeed, the efficiency of photocatalytic Bi-N-TiO2 as a visible light is shown by a complete discoloration of indigo carmine solution of 16 mg/L after 40 minutes, whereas with the P25-TiO2 discoloration is achieved after 90 minutes.

Keywords: POA, heterogeneous photocatalysis, TiO2, co-doping

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Authors: Magdalena Diaka, Paweł Mazierski, Joanna Żebrowska, Michał Winiarski, Tomasz Klimczuk, Adriana Zaleska-Medynska

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During the last years, TiO2 nanotubes have been widely studied due to their unique highly ordered array structure, unidirectional charge transfer and higher specific surface area compared to conventional TiO2 powder. These photoactive materials, in the form of thin layer, can be activated by low powered and low cost irradiation sources (such as LEDs) to remove VOCs, microorganism and to deodorize air streams. This is possible due to their directly growth on a support material and high surface area, which guarantee enhanced photon absorption together with an extensive adsorption of reactant molecules on the photocatalyst surface. TiO2 nanotubes exhibit also lots of other attractive properties, such as potential enhancement of electron percolation pathways, light conversion, and ion diffusion at the semiconductor-electrolyte interface. Pure TiO2 nanotubes were previously used to remove organic compounds from the gas phase as well as in water splitting reaction. The major factors limiting the use of TiO2 nanotubes, which have not been fully overcome, are their relatively large band gap (3-3,2 eV) and high recombination rate of photogenerated electron–hole pairs. Many different strategies were proposed to solve this problem, however titania nanostructures containing incorporated metal oxides like Ag2O shows very promising, new optical and photocatalytic properties. Unfortunately, there is still very limited number of reports regarding application of TiO2/MxOy nanostructures. In the present work, we prepared TiO2/Ag2O nanotubes obtained by anodization of Ti-Ag alloys containing 5, 10 and 15 wt. % Ag. Photocatalysts prepared in this way were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), luminescence spectroscopy and UV-Vis spectroscopy. The activities of new TiO2/Ag2O were examined by photocatalytic degradation of toluene in gas phase reaction and phenol in aqueous phase using 1000 W Xenon lamp (Oriel) and light emitting diodes (LED) as a irradiation sources. Additionally efficiency of bacteria (Pseudomonas aeruginosa) removal from the gas phase was estimated. The number of surviving bacteria was determined by the serial twofold dilution microtiter plate method, in Tryptic Soy Broth medium (TSB, GibcoBRL).

Keywords: photocatalysis, antibacterial properties, titania nanotubes, new TiO2/MxOy nanostructures

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Authors: Friday Godwin Okibe, Elaoyi David Paul, Oladayo Thomas Ojekunle

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In this study, Nitrogen and Phosphorous co-doped Zinc Oxide (NPZ) was prepared through a solvent-free reaction. The NPZ was characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy. The photocatalytic activity of the catalyst was investigated by monitoring the degradation of para-nitrophenol (PNP) under visible light irradiation and the process was optimized using factorial design of experiment. The factors investigated were initial concentration of para-nitrophenol, catalyst loading, pH and irradiation time. The characterization results revealed a successful doping of ZnO by nitrogen and phosphorus and an improvement in the surface morphology of the catalyst. The photo-catalyst exhibited improved photocatalytic activity under visible light by 73.8%. The statistical analysis of the optimization result showed that the model terms were significant at 95% confidence level. Interactions plots revealed that irradiation time was the most significant factor affecting the degradation process. The cube plots of the interactions of the variables showed that an optimum degradation efficiency of 66.9% was achieved at 10mg/L initial PNP concentration, 0.5g catalyst loading, pH 7 and 150 minutes irradiation time.

Keywords: nitrogen and phosphorous co-doped Zno, p-nitrophenol, photocatalytic degradation, optimization, factorial design of experimental

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Authors: Thabelo Nelushi, Michael Scurrell, Tumelo Seadira

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Global warming is one of the most important environmental issues which arise from occurrence of gases such as carbon dioxide (CO2) and methane (CH4) in the atmosphere. Exposure to these greenhouse gases results in health risk. Hydrogen is regarded as an alternative energy source which is a clean energy carrier for the future. There are different methods to produce hydrogen such as steam reforming, coal gasification etc., however the challenge with these processes is that they emit CO and CO2 gases and are costly. Photocatalytic reforming is a substitute process which is fascinating due to the combination of solar energy and renewable sources and the use of semiconductor materials such as catalysts. TiO2 is regarded as the most promising catalysts. TiO2 nanoparticles prepared by hydrothermal method and Ag/TiO2 are being investigated for photocatalytic production of hydrogen from butanol. The samples were characterized by raman spectroscopy, TEM/SEM, XRD, XPS, EDAX, DRS and BET surface area. 2 wt% Ag-doped TiO2 nanoparticle showed enhanced hydrogen production compared to a non-doped TiO2. The results of characterization and photoactivity shows that TiO2 nanoparticles play a very important role in producing high hydrogen by utilizing solar irradiation.

Keywords: butanol, hydrogen production, silver particles, TiO2 nanoparticles

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Authors: Payam Hayati, Fateme Firoozbakht, Gholamhassan Azimi, Shahram Tangestaninejad

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The synthesis of a photocatalytic adsorbent involved the integration of carbon dots (CD) into a metal-organic framework (MOF) of MIL-88B(Fe) using the solvothermal technique. Characterization of the resulting CD@MIL-88B(Fe) was conducted using various analytical methods, including X-ray-based microscopic and spectroscopic techniques, electrochemical impedance spectroscopy, UV–Vis, FT-IR, DRS, TGA, and photoluminescence (PL) analysis. The adsorbent demonstrated significant photocatalytic activity, achieving up to 92% and 90% removal of amphotericin B (AmB) and naproxen (Nap) from aqueous solutions under visible light, with an RSD value of around 5%. The study explored the factors influencing the degradation of pharmaceuticals and determined the optimal conditions for the process, including pH values of 3 and 4 for AmB and Nap, a photocatalyst concentration of 0.2 g L-1, and an H2O2 concentration ranging from 40 to 50 mM. Reactive oxidative species such as ⋅OH and ⋅O2 were identified through the examination of different scavengers. Additionally, the adsorption isotherm and kinetic studies revealed that the synthesized photocatalyst functions as an effective adsorbent, with maximum adsorption capacities of 42.5 and 121.5 mg g-1 for AmB and Nap, while also serving as a photocatalytic agent for removal purposes.

Keywords: fenton-like degradation, metal-organic frameworks, heterogenous photocatalysts, naproxen

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Authors: S. K. M. Nzaba, H. H. Nyoni, B. Ntsendwana, B. B. Mamba, A. T. Kuvarega

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Azo dye effluents, released into water bodies are not only toxic to the ecosystem but also pose a serious impact on human health due to the carcinogenic and mutagenic effects of the compounds present in the dye discharge. Conventional water treatment methods such as adsorption, flocculation/coagulation and biological processes are not effective in completely removing most of the dyes and their natural degradation by-products. Advanced oxidation processes (AOPs) have proven to be effective technologies for complete mineralization of these recalcitrant pollutants. Therefore, there is a need for new technology that can solve the problem. Thus, this study examined the photocatalytic degradation of an azo dye brilliant black (BB) using non-metal/metal codoped TiO₂. N, Pt co-doped TiO₂ photocatalysts were prepared by a modified sol-gel method using amine-terminated polyamidoamine dendrimer generation 0 (PAMAM G0), amine-terminated polyamidoamine dendrimer generation 1 ( PAMAM G1) and hyperbranched polyethyleneimine (HPEI) as templates and source of nitrogen. Structural, morphological, and textural properties were evaluated using scanning electron microscopy coupled to energy dispersive X-ray spectroscopy (SEM/EDX), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), Fourier- transform infrared (FTIR), Raman spectroscopy (RS), photoluminescence (PL) and ultra-violet /visible spectroscopy (UV-Vis). The synthesized photocatalysts exhibited lower band gap energies as compared to the Degussa P-25 revealing a red shift in band gap towards the visible light absorption region. Photocatalytic activity of N, Pt co-doped TiO₂ was measured by the reaction of photocatalytic degradation of brilliant black (BB) dye. The N, metal codoped TiO₂ containing 0.5 wt. % of the metal consisted mainly of the anatase phase as confirmed by XRD results of all three samples, with a particle size range of 13–30 nm. The particles were largely spherical and shifted the absorption edge well into the visible region. Band gap reduction was more pronounced for the N, Pt HPEI (Pt 0.5 wt. %) codoped TiO₂ compared to PAMAM G0 and PAMAM G1. Consequently, codoping led to an enhancement in the photocatalytic activity of the materials for the degradation of brilliant black (BB).

Keywords: codoped TiO₂, dendrimer, photodegradation, wastewater

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Authors: Amina Adala, Nadra Debbache, Tahar Sehili

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Coordination polymers and uniformly {[Zn(II)(BIPY)(Pht)]n} (1), {[Zn (HYD)(Pht)]n} (2) (BIPY = 4,4’ bipyridine, Pht = terephtalic acid, HYD = 8-hydroxyquinoline) have been successfully synthesized by a hydrothermal process using aqueous zinc solution. The as-prepared compounds phases were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy, UV-visible spectroscopy, thermogravimetric analysis (TGA), and the electrochemistry study by the voltammetry cyclic. The results showed a crystalline phase for CP1 however, CP2 requires recrystallization; the FTIR showed the presence of characteristic bands of all ligands; besides that, TGA shows thermal stability up to 300°C. The electrochemistry study showed a good charge transfer between the ligands and Zn metal for the two components. UV-Vis measurement showed strong absorption in a wide range from UV to visible light with a band gap of 2.69 eV for CP1 and 2.56 eV for CP2, smaller than that of ZnO. This represents an alternative to using ZnO. The Ibuprofen IBP decomposition kinetics of 5.10⁻⁵ mol.L⁻¹ under solar and artificial light were studied for different irradiation conditions. Good photocatalytic properties were observed due to their high surface area.

Keywords: metal-organic frameworks, photocatalysis, photodegradation, organic pollutant, ibuprofen

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Authors: Saba Didarataee, Abbas Ali Khodadadi, Yadollah Mortazavi, Fatemeh Mousavi

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Photocatalytic water splitting is one of the most attractive alternative methods for hydrogen evolution. A variety of nanoparticle engineering techniques were introduced to improve the activity of semiconductor photocatalysts. Among these methods, heterojunction formation is an appealing method due to its ability to effectively preventing electron-hole recombination and improving photocatalytic activity. Reaching an optimal ratio of the two target semiconductors for the formation of heterojunctions is still an open question. Considering environmental issues as well as the cost and availability, ZnS and ZnO are frequently studied as potential choices. In this study, first, the ZnS nanoparticle was synthesized in a hydrothermal process; the formation of ZnS nanorods with a diameter of 14-30 nm was confirmed by field emission scanning electron microscope (FESEM). Then two different methods, partial oxidation and chemical precipitation were employed to construct ZnS/ZnO core-shell heterojunction. X-ray diffraction (XRD), BET, and diffuse reflectance spectroscopy (DRS) analysis were carried out to determine crystallite phase, surface area, and bandgap of photocatalysts. Furthermore, the temperature of oxidation was specified by a temperature programmed oxidation (TPO) and was fixed at 510℃, at which mild oxidation occurred. The bandgap was calculated by the Kubelka-Munk method and decreased by increasing oxide content from 3.53 (pure ZnS) to 3.18 (pure ZnO). The optimal samples were determined by testing the photocatalytic activity of hydrogen evolution in a quartz photoreactor with side irradiation of UVC lamps with a wavelength of 254 nm. In both procedures, it was observed that the photocatalytic activity of the ZnS/ZnO composite was sensibly higher than the pure ZnS and ZnO, which is attributed to forming a type-II heterostructure. The best ratio of oxide to sulfide was 0.24 and 0.37 in partial oxidation and chemical precipitation, respectively. The highest hydrogen evolution was 1081 µmol/gr.h, gained from partial oxidizing of ZnS nanoparticles at 510℃ for 30 minutes.

Keywords: heterostructure, hydrogen, partial oxidation, photocatalyst, water splitting, ZnS

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Authors: M. S. Abd El-Sadek, M. A. Omar, Gharib M. Taha

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In recent years, photocatalytic degradation of various kinds of organic and inorganic pollutants using semiconductor powders as photocatalysts has been extensively studied. Owing to its relatively high photocatalytic activity, biological and chemical stability, low cost, nonpoisonous and long stable life, Tin oxide materials have been widely used as catalysts in chemical reactions, including synthesis of vinyl ketone, oxidation of methanol and so on. Tin oxide (SnO₂), with a rutile-type crystalline structure, is an n-type wide band gap (3.6 eV) semiconductor that presents a proper combination of chemical, electronic and optical properties that make it advantageous in several applications. In the present work, SnO₂ nanoparticles were synthesized at room temperature by the sol-gel process and thermohydrolysis of SnCl₂ in isopropanol by controlling the crystallite size through calculations. The synthesized nanoparticles were identified by using XRD analysis, TEM, FT-IR, and Uv-Visible spectroscopic techniques. The crystalline structure and grain size of the synthesized samples were analyzed by X-Ray diffraction analysis (XRD) and the XRD patterns confirmed the presence of tetragonal phase SnO₂. In this study, Methylene blue degradation was tested by using SnO₂ nanoparticles (at different calculations temperatures) as a photocatalyst under sunlight as a source of irradiation. The results showed that the highest percentage of degradation of Methylene blue dye was obtained by using SnO₂ photocatalyst at calculations temperature 800 ᵒC. The operational parameters were investigated to be optimized to the best conditions which result in complete removal of organic pollutants from aqueous solution. It was found that the degradation of dyes depends on several parameters such as irradiation time, initial dye concentration, the dose of the catalyst and the presence of metals such as silver as a dopant and its concentration. Percent degradation was increased with irradiation time. The degradation efficiency decreased as the initial concentration of the dye increased. The degradation efficiency increased as the dose of the catalyst increased to a certain level and by further increasing the SnO₂ photocatalyst dose, the degradation efficiency is decreased. The best degradation efficiency on which obtained from pure SnO₂ compared with SnO₂ which doped by different percentage of Ag.

Keywords: SnO₂ nanoparticles, a sol-gel method, photocatalytic applications, methylene blue, degradation efficiency

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